Production of renewable polymers from crop plants.

Plants produce a range of biopolymers for purposes such as maintenance of structural integrity, carbon storage, and defense against pathogens and desiccation. Several of these natural polymers are used by humans as food and materials, and increasingly as an energy carrier. In this review, we focus on plant biopolymers that are used as materials in bulk applications, such as plastics and elastomers, in the context of depleting resources and climate change, and consider technical and scientific bottlenecks in the production of novel or improved materials in transgenic or alternative crop plants. The biopolymers discussed are natural rubber and several polymers that are not naturally produced in plants, such as polyhydroxyalkanoates, fibrous proteins and poly-amino acids. In addition, monomers or precursors for the chemical synthesis of biopolymers, such as 4-hydroxybenzoate, itaconic acid, fructose and sorbitol, are discussed briefly.

[1]  Rima Menassa,et al.  Spider dragline silk proteins in transgenic tobacco leaves: accumulation and field production. , 2004, Plant biotechnology journal.

[2]  H. Mooibroek,et al.  Alternative sources of natural rubber , 2000, Applied Microbiology and Biotechnology.

[3]  K. Cornish Biochemistry of natural rubber, a vital raw material, emphasizing biosynthetic rate, molecular weight and compartmentalization, in evolutionarily divergent plant species. , 2001, Natural product reports.

[4]  H. Nakashita,et al.  Plastid Targeting of Polyhydroxybutyrate Biosynthetic Pathway in Tobacco , 2001 .

[5]  J. Oszmiański,et al.  Engineering of PHB Synthesis Causes Improved Elastic Properties of Flax Fibers , 2007, Biotechnology progress.

[6]  R. Visser,et al.  Transgene Organisation in Potato After Particle Bombardment-mediated (co-)Transformation Using Plasmids and Gene Cassettes , 2003, Transgenic Research.

[7]  D. E. Van Dyk,et al.  Metabolic Engineering of the Chloroplast Genome Using the Echerichia coli ubiC Gene Reveals That Chorismate Is a Readily Abundant Plant Precursor for p-Hydroxybenzoic Acid Biosynthesis1 , 2004, Plant Physiology.

[8]  Joerg M. Buescher,et al.  Microbial Biosynthesis of Polyglutamic Acid Biopolymer and Applications in the Biopharmaceutical, Biomedical and Food Industries , 2007, Critical reviews in biotechnology.

[9]  Alison M. Smith Prospects for increasing starch and sucrose yields for bioethanol production. , 2008, The Plant journal : for cell and molecular biology.

[10]  K. Baier,et al.  Biosynthesis of the cyanobacterial reserve polymer multi-L-arginyl-poly-L-aspartic acid (cyanophycin): mechanism of the cyanophycin synthetase reaction studied with synthetic primers. , 2000, European journal of biochemistry.

[11]  S. Taguchi,et al.  Synthesis of Short-chain-length/Medium-chain-length Polyhydroxyalkanoate (PHA) Copolymers in Peroxisome of the Transgenic Arabidopsis Thaliana Harboring the PHA Synthase Gene from Pseudomonas sp. 61-3 , 2006 .

[12]  J. Scheller,et al.  Production of spider silk proteins in tobacco and potato , 2001, Nature Biotechnology.

[13]  Markus Pauly,et al.  Cell-wall carbohydrates and their modification as a resource for biofuels. , 2008, The Plant journal : for cell and molecular biology.

[14]  K. Cornish,et al.  Similarities and differences in rubber biochemistry among plant species. , 2001, Phytochemistry.

[15]  Fritz Vollrath,et al.  Liquid crystalline spinning of spider silk , 2001, Nature.

[16]  Qing Yang,et al.  Synthesis of medium-chain-length-polyhydroxyalkanoates in tobacco via chloroplast genetic engineering , 2005 .

[17]  Sheryl E. Philip,et al.  Polyhydroxyalkanoates: biodegradable polymers with a range of applications , 2007 .

[18]  J. Sanders,et al.  Protamylasse, a Residual Compound of Industrial Starch Production, Provides a Suitable Medium for Large-Scale Cyanophycin Production , 2005, Applied and Environmental Microbiology.

[19]  S. Mecking,et al.  Nature or petrochemistry?-biologically degradable materials. , 2004, Angewandte Chemie.

[20]  R. Weusthuis,et al.  Properties, modifications and applications of biopolyesters. , 2001, Advances in biochemical engineering/biotechnology.

[21]  Seungdo Kim,et al.  Life Cycle Assessment Study of Biopolymers (Polyhydroxyalkanoates) - Derived from No-Tilled Corn (11 pp) , 2005 .

[22]  D. Kaplan,et al.  Biosynthesis and Applications of Silk‐like and Collagen‐like Proteins , 2007 .

[23]  L. Willmitzer,et al.  Constitutive Expression of the β-Ketothiolase Gene in Transgenic Plants. A Major Obstacle for Obtaining Polyhydroxybutyrate-Producing Plants1 , 2002, Plant Physiology.

[24]  Y. Poirier,et al.  Polyhydroxyalkanoate synthesis in transgenic plants as a new tool to study carbon flow through beta-oxidation. , 1999, The Plant journal : for cell and molecular biology.

[25]  A. Anderson,et al.  Occurrence, metabolism, metabolic role, and industrial uses of bacterial polyhydroxyalkanoates. , 1990, Microbiological reviews.

[26]  A. Flahault,et al.  Natural rubber latex allergy among health care workers: a systematic review of the evidence. , 2006, The Journal of allergy and clinical immunology.

[27]  Y. Poirier Polyhydroxyalknoate synthesis in plants as a tool for biotechnology and basic studies of lipid metabolism. , 2002, Progress in lipid research.

[28]  G. Galili,et al.  Improving the levels of essential amino acids and sulfur metabolites in plants , 2005, Biological chemistry.

[29]  S. Smeekens,et al.  Engineering fructan metabolism in plants. , 2003, Journal of plant physiology.

[30]  M. Devine Why are there not more herbicide-tolerant crops? , 2005, Pest management science.

[31]  I. Shih,et al.  Microbial synthesis of poly(ε-lysine) and its various applications , 2006 .

[32]  A. Steinbüchel,et al.  Occurrence, functions and biosynthesis of polyamides in microorganisms and biotechnological production , 2001, Naturwissenschaften.

[33]  Alexander Steinbüchel,et al.  Increased diversification of polyhydroxyalkanoates by modification reactions for industrial and medical applications , 2007, Applied Microbiology and Biotechnology.

[34]  T. Koyama,et al.  Molecular cloning, expression and characterization of cDNA encoding cis-prenyltransferases from Hevea brasiliensis. A key factor participating in natural rubber biosynthesis. , 2003, European journal of biochemistry.

[35]  L. Bedzyk,et al.  Production of synthetic spider dragline silk protein in Pichia pastoris , 1997, Applied Microbiology and Biotechnology.

[36]  I. Noda,et al.  Preparation and properties of a novel class of polyhydroxyalkanoate copolymers. , 2005, Biomacromolecules.

[37]  M. E. John,et al.  Cotton Crop Improvement Through Genetic Engineering , 1997 .

[38]  S. Taguchi,et al.  PHA synthase engineering toward superbiocatalysts for custom-made biopolymers , 2007, Applied Microbiology and Biotechnology.

[39]  R. Bock Plastid biotechnology: prospects for herbicide and insect resistance, metabolic engineering and molecular farming. , 2007, Current opinion in biotechnology.

[40]  Johnathan E. Holladay,et al.  Top Value Added Chemicals From Biomass. Volume 1 - Results of Screening for Potential Candidates From Sugars and Synthesis Gas , 2004 .

[41]  Chris Holland,et al.  Natural and unnatural silks , 2007 .

[42]  D. Argyropoulos,et al.  Chemicals and energy from biomass , 2006 .

[43]  W. Orts,et al.  Thermoformed wheat gluten biopolymers. , 2006, Journal of agricultural and food chemistry.

[44]  R. Marchessault,et al.  Bacterial polyesters: biosynthesis, biodegradable plastics and biotechnology. , 2005, Biomacromolecules.

[45]  J. Sanders,et al.  Biomass in the manufacture of industrial products—the use of proteins and amino acids , 2007, Applied Microbiology and Biotechnology.

[46]  M. Yasuda,et al.  Synthesis of a novel class of polyhydroxyalkanoates in Arabidopsis peroxisomes, and their use in monitoring short-chain-length intermediates of beta-oxidation. , 2002, Plant & cell physiology.

[47]  Hans Mooibroek,et al.  Bio-refinery as the bio-inspired process to bulk chemicals. , 2007, Macromolecular bioscience.

[48]  J. Szopa,et al.  Polyhydroxybutyrate synthesis in transgenic flax. , 2004, Journal of biotechnology.

[49]  U. Conrad,et al.  Compartment-specific accumulation of recombinant immunoglobulins in plant cells: an essential tool for antibody production and immunomodulation of physiological functions and pathogen activity , 1998, Plant Molecular Biology.

[50]  E. Atwill,et al.  Neonatal-Mouse Infectivity of Intact Cryptosporidium parvum Oocysts Isolated after Optimized In Vitro Excystation , 2004, Applied and Environmental Microbiology.

[51]  Daisuke Tsuchiya,et al.  Structural basis for channelling mechanism of a fatty acid β‐oxidation multienzyme complex , 2004, The EMBO journal.

[52]  A. Steinbüchel,et al.  Diversity of bacterial polyhydroxyalkanoic acids , 1995 .

[53]  Manoj Kumar,et al.  New proteins in a materials world. , 2005, Current opinion in biotechnology.

[54]  Matthew A. Collin,et al.  Blueprint for a High-Performance Biomaterial: Full-Length Spider Dragline Silk Genes , 2007, PloS one.

[55]  Y. Poirier,et al.  Synthesis of medium-chain-length polyhydroxyalkanoates in arabidopsis thaliana using intermediates of peroxisomal fatty acid beta-oxidation. , 1998, Proceedings of the National Academy of Sciences of the United States of America.

[56]  M. E. John,et al.  Metabolic pathway engineering in cotton: biosynthesis of polyhydroxybutyrate in fiber cells. , 1996, Proceedings of the National Academy of Sciences of the United States of America.

[57]  J. Scheller,et al.  Purification of Spider Silk-elastin from Transgenic Plants and Application for Human Chondrocyte Proliferation , 2004, Transgenic Research.

[58]  Y. Poirier Production of new polymeric compounds in plants. , 1999, Current opinion in biotechnology.

[59]  T. Scheibel Protein fibers as performance proteins: new technologies and applications. , 2005, Current opinion in biotechnology.

[60]  B. Witholt,et al.  Expression of poly-3-(R)-hydroxyalkanoate (PHA) polymerase and acyl-CoA-transacylase in plastids of transgenic potato leads to the synthesis of a hydrophobic polymer, presumably medium-chain-length PHAs , 2004, Planta.

[61]  W. Lockau,et al.  Plastid targeting strategies for cyanophycin synthetase to achieve high-level polymer accumulation in Nicotiana tabacum. , 2008, Plant biotechnology journal.

[62]  K. Chow,et al.  Transcriptome analysis reveals novel features of the molecular events occurring in the laticifers of Hevea brasiliensis (para rubber tree) , 2003, Plant Molecular Biology.

[63]  D. Stark,et al.  PHA production, from bacteria to plants. , 1999, International Journal of Biological Macromolecules.

[64]  S. Fahnestock,et al.  Synthetic spider dragline silk proteins and their production in Escherichia coli , 1997, Applied Microbiology and Biotechnology.

[65]  R. Trethewey,et al.  Transgenic Arabidopsis plants can accumulate polyhydroxybutyrate to up to 4% of their fresh weight , 2000, Planta.

[66]  Witholt,et al.  Perspectives of medium chain length poly(hydroxyalkanoates), a versatile set of bacterial bioplastics , 1999, Current opinion in biotechnology.

[67]  L. Nielsen,et al.  Production of polyhydroxybutyrate in sugarcane. , 2007, Plant biotechnology journal.

[68]  F. Doaré,et al.  Bypassing of a polygenic Microcyclus ulei resistance in rubber tree, analyzed by QTL detection. , 2007, The New phytologist.

[69]  A. Steinbüchel,et al.  Application of the BPEC Pathway for Large-Scale Biotechnological Production of Poly(3-Mercaptopropionate) by Recombinant Escherichia coli, Including a Novel In Situ Isolation Method , 2005, Applied and Environmental Microbiology.

[70]  K. Houmiel,et al.  Poly(β-hydroxybutyrate) production in oilseed leukoplasts of Brassica napus , 1999, Planta.

[71]  Loren G. Polhamus Rubber : botany, production and utilization , 1962 .

[72]  Zhan-Bin Liu,et al.  High yield recombinant silk-like protein production in transgenic plants through protein targeting , 2005, Transgenic Research.

[73]  K. Cornish,et al.  Absence of cross-reactivity of IgE antibodies from subjects allergic to Hevea brasiliensis latex with a new source of natural rubber latex from guayule (Parthenium argentatum). , 1996, The Journal of allergy and clinical immunology.

[74]  John W. Lawton,et al.  Zein: a history of processing and use , 2002 .

[75]  Chris Somerville,et al.  Production of Polyhydroxyalkanoates, a Family of Biodegradable Plastics and Elastomers, in Bacteria and Plants , 1995, Bio/Technology.

[76]  Steven C. Slater,et al.  Greenhouse Gas Profile of a Plastic Material Derived from a Genetically Modified Plant , 2000 .

[77]  C. Guda,et al.  Stable expression of a biodegradable protein-based polymer in tobacco chloroplasts , 2000, Plant Cell Reports.

[78]  T. Gerngross,et al.  Can biotechnology move us toward a sustainable society? , 1999, Nature Biotechnology.

[79]  K. Shinozaki,et al.  Engineering drought tolerance in plants: discovering and tailoring genes to unlock the future. , 2006, Current opinion in biotechnology.

[80]  F. Cataldo,et al.  Guayule rubber : A new possible world scenario for the production of natural rubber? , 2000 .

[81]  J. Scheller,et al.  Plant-based material, protein and biodegradable plastic. , 2005, Current opinion in plant biology.

[82]  Y. Poirier,et al.  Pathways for the Synthesis of Polyesters in Plants: Cutin, Suberin, and Polyhydroxyalkanoates , 2008 .

[83]  T. Fukui,et al.  Production of Biodegradable Polyester by a Transgenic Tobacco. , 1999, Bioscience, biotechnology, and biochemistry.

[84]  M. G. O'shea,et al.  Growth and metabolism in sugarcane are altered by the creation of a new hexose-phosphate sink. , 2007, Plant biotechnology journal.

[85]  C. Gong,et al.  Production of multifunctional organic acids from renewable resources. , 1999, Advances in biochemical engineering/biotechnology.

[86]  M. Theisen,et al.  Triple helix assembly and processing of human collagen produced in transgenic tobacco plants , 2000, FEBS letters.

[87]  M B Hinman,et al.  Synthetic spider silk: a modular fiber. , 2000, Trends in biotechnology.

[88]  A. Linnemann,et al.  Towards Sustainable Production of Protein-Rich Foods: Appraisal of Eight Crops for Western Europe. PART II: Analysis of the Technological Aspects of the Production Chain , 2003, Critical reviews in food science and nutrition.

[89]  K. Kiick Biosynthetic Methods for the Production of Advanced Protein‐Based Materials , 2007 .

[90]  F. Srienc,et al.  Peroxisomes as Sites for Synthesis of Polyhydroxyalkanoates in Transgenic Plants , 1999, Biotechnology progress.

[91]  J. B. van Beilen,et al.  Establishment of new crops for the production of natural rubber. , 2007, Trends in biotechnology.

[92]  Yuriy Román-Leshkov,et al.  Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose , 2006, Science.

[93]  E. Chaikof,et al.  Protein-Based Thermoplastic Elastomers , 2005 .

[94]  A. Sinskey,et al.  Nontemplate-dependent polymerization processes: polyhydroxyalkanoate synthases as a paradigm. , 2005, Annual review of biochemistry.

[95]  G. Wenzel Molecular plant breeding: achievements in green biotechnology and future perspectives , 2006, Applied Microbiology and Biotechnology.

[96]  G. Huisman,et al.  Formation of Polyesters by Pseudomonas oleovorans: Effect of Substrates on Formation and Composition of Poly-(R)-3-Hydroxyalkanoates and Poly-(R)-3-Hydroxyalkenoates , 1988, Applied and environmental microbiology.

[97]  L. A. Petrasovits,et al.  Developing the sugarcane biofactory for high-value biomaterials , 2005 .

[98]  F. Srienc,et al.  Production of a Biodegradable Plastic Polymer, Poly‐β‐Hydroxybutyrate, in Transgenic Alfalfa , 2002 .

[99]  Y. Poirier,et al.  Targeting of the polyhydroxybutyrate biosynthetic pathway to the plastids of Arabidopsis thaliana results in high levels of polymer accumulation. , 1994, Proceedings of the National Academy of Sciences of the United States of America.

[100]  W. Lockau,et al.  Production of cyanophycin, a suitable source for the biodegradable polymer polyaspartate, in transgenic plants. , 2005, Plant biotechnology journal.

[101]  G. Kishore,et al.  Metabolic engineering of Arabidopsis and Brassica for poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer production , 1999, Nature Biotechnology.

[102]  Wanjun Liu,et al.  Soy Protein-Based Plastics, Blends, and Composites , 2005 .

[103]  J. B. van Beilen,et al.  Guayule and Russian Dandelion as Alternative Sources of Natural Rubber , 2007, Critical reviews in biotechnology.

[104]  Munir Cheryan,et al.  Zein: the industrial protein from corn , 2001 .

[105]  H. Koop,et al.  Polyester synthesis in transplastomic tobacco (Nicotiana tabacum L.): significant contents of polyhydroxybutyrate are associated with growth reduction , 2003, Plant Cell Reports.

[106]  K. Vorlop,et al.  Biotechnological production of itaconic acid , 2001, Applied Microbiology and Biotechnology.

[107]  L. Heide,et al.  Genetic Engineering of Plant Secondary Metabolism (Accumulation of 4-Hydroxybenzoate Glucosides as a Result of the Expression of the Bacterial ubiC Gene in Tobacco) , 1996, Plant physiology.

[108]  D. E. Van Dyk,et al.  Initial evaluation of sugarcane as a production platform for p-hydroxybenzoic acid. , 2004, Plant biotechnology journal.

[109]  Steven Arcidiacono,et al.  Spider Silk Fibers Spun from Soluble Recombinant Silk Produced in Mammalian Cells , 2002, Science.

[110]  C. Jung,et al.  Expression of bacterial poly(3-hydroxybutyrate) synthesis genes in hairy roots of sugar beet (Beta vulgaris L.) , 2002, Applied Microbiology and Biotechnology.

[111]  Eve Syrkin Wurtele,et al.  Reverse Genetic Characterization of Cytosolic Acetyl-CoA Generation by ATP-Citrate Lyase in Arabidopsisw⃞ , 2005, The Plant Cell Online.

[112]  Y. Poirier,et al.  Polyhydroxybutyrate, a Biodegradable Thermoplastic, Produced in Transgenic Plants , 1992, Science.